Dual function composite oxygen transport membrane

• US 10,441,922 B2
• Filed: 06/29/2015
• Issued: 10/15/2019
• Est. Priority Date: 06/29/2015
• Status: Active Grant

• Current Assignee: Praxair Technology Incorporated (Linde Plc)
• Original Assignee: Praxair Technology Incorporated (Linde Plc)
• Inventors: Lin, Jiefeng, Plonczak, Pawel, Kelly, Sean M., Doraswami, Uttam R., Lane, Jonathan A.
• Primary Examiner(s): Sample, David
• Assistant Examiner(s): Omori, Mary I
• Application Number:
  US14/753,815
• Publication Number:
  US 20160375411A1
• Time in Patent Office: 1,569 Days
• Field of Search: None
• CPC Class Codes: B01D 2311/2696 Catalytic reactions
• CPC Class Codes: B01D 2325/10 Catalysts being present on the surface of the membrane or in the pores
• CPC Class Codes: B01D 2325/20 Specific permeability or cut-off range
• CPC Class Codes: B01D 53/228 characterised by specific membranes
• CPC Class Codes: B01D 67/0039 Inorganic membrane manufacture
• CPC Class Codes: B01D 67/0048 by sol-gel transition
• CPC Class Codes: B01D 69/04 Tubular membranes
• CPC Class Codes: B01D 69/10 Supported membranes; Membrane supports
• CPC Class Codes: B01D 69/108 Inorganic support material
• CPC Class Codes: B01D 69/12 Composite membranes; Ultra-thin membranes
• CPC Class Codes: B01D 69/1216 Three or more layers
• CPC Class Codes: B01D 71/02231 Palladium
• CPC Class Codes: B01D 71/024 Oxides
• CPC Class Codes: B01D 71/0271 Perovskites
• CPC Class Codes: B01J 23/462 Ruthenium
• CPC Class Codes: B01J 23/892 Nickel and noble metals
• CPC Class Codes: B01J 35/59 Membranes
• CPC Class Codes: B01J 37/0215 Coating
• CPC Class Codes: Y02E 60/50 Fuel cells

Abstract

A dual function composite oxygen transport membrane having a layered structure of mixed conducting oxygen transport materials on a first side of a porous substrate and a reforming catalyst layer on an opposing second side of the porous substrate. The layered structure of the mixed conducting oxygen transport materials contains an intermediate porous layer of mixed conducting oxygen transport materials formed on the porous substrate with a dense impervious layer of mixed conducting oxygen transport materials over the intermediate porous layer, and an optional surface exchange layer of mixed conducting oxygen transport materials over the dense impervious layer. The layered structure and the reforming catalyst layer are formed in separate steps.

Claims

1. A dual function composite oxygen transport membrane, said dual function membrane comprising:

a porous substrate having a first side and an opposing side, a plurality of mixed conducting oxygen transport layers, and a catalyst layer for catalyzing endothermic reactions, wherein the plurality of mixed conducting oxygen transport layers are formed on the first side of the porous substrate and the catalyst layer is coated on the opposing second side of the porous substrate, wherein a thickness of the catalyst layer is at least 10 microns.

2. The dual function composite oxygen transport membrane of claim 1 wherein said plurality of mixed conducting oxygen transport layers form a layered structure comprising a dense layer, an intermediate porous layer located between the dense layer and the porous substrate, and an optional surface exchange layer over the dense layer wherein each of the dense layer and the intermediate porous layer and the surface exchange layer are capable of conducting oxygen ions and electrons at operational temperatures.

3. The dual function composite oxygen transport membrane of claim 2 wherein said layered structure formed on the first side of the porous substrate separates oxygen from an oxygen containing gas stream in contact with the layered structure when operational at operational temperatures and provide said separated oxygen for reaction with a combustible substance diffusing through the catalyst layer formed on the opposing second side of said porous substrate.

4. The dual function composite oxygen transport membrane of claim 1 wherein, the thickness of said catalyst layer is in the range of about 40 microns to about 80 microns.

5. The dual function composite oxygen transport membrane of claim 1 wherein the catalyst layer contains one or more of nickel, rhodium, platinum, ruthenium, or palladium.

6. The dual function composite oxygen transport membrane of claim 1 wherein the catalyst layer is formed using precursors of nickel or rhodium or platinum or ruthenium or palladium or mixtures of two or more thereof.

7. The dual function composite oxygen transport membrane of claim 1 wherein the catalyst layer is formed using a perovskite material containing Ruthenium.

8. The dual function composite oxygen transport membrane of claim 1 further comprising the porous substrate configured as a substantially tubular structure wherein the plurality of mixed conducting oxygen transport layers are formed on the outside surface of said tubular structure and the catalyst layer is formed on the inside surface of said tubular structure.

9. A method of forming a dual function composite oxygen transport membrane, said method comprising:

providing a porous substrate having a first side and an opposing second side;

forming a layer structure of mixed conducting materials in a sintered state on the first side of the porous substrate, coating a catalyst layer on the opposing second side of the porous substrate for catalyzing endothermic reactions, wherein a thickness of the catalyst layer is at least 10 microns.

10. The method of claim 9 wherein the layered structure of mixed conducting materials comprises an intermediate porous layer, a dense layer, and an optional surface exchange layer, and the forming of the dense layer and the forming of the catalyst layer is carried out in separate steps.

11. A method of forming a dual function composite oxygen transport membrane, said method comprising:

providing a porous substrate having a first side and an opposing second side;

forming an intermediate porous layer on the first side of the porous substrate;

forming a dense layer over the intermediate porous layer, forming a surface exchange layer over the dense layer, and coating a catalyst layer on the opposing second side of the porous substrate, wherein a thickness of the catalyst layer is at least 10 microns.

12. The method of claim 11 wherein the coating of the catalyst layer is carried out after the forming of the surface exchange layer.

13. The method of claim 11 wherein a catalyst layer coating step in the coating of the catalyst layer is carried out prior to a high temperature sintering step in the forming of the surface exchange layer.

14. The method of claim 11 wherein a catalyst layer coating step in the coating of the catalyst layer is carried out prior to a coating step in the forming of the surface exchange layer.

15. The method of claim 11 wherein a catalyst layer coating step in the coating of the catalyst layer is a wash-coating technique.